WO2015005235A1 - Glass - Google Patents
Glass Download PDFInfo
- Publication number
- WO2015005235A1 WO2015005235A1 PCT/JP2014/067889 JP2014067889W WO2015005235A1 WO 2015005235 A1 WO2015005235 A1 WO 2015005235A1 JP 2014067889 W JP2014067889 W JP 2014067889W WO 2015005235 A1 WO2015005235 A1 WO 2015005235A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- glass
- sio
- cao
- temperature
- mgo
- Prior art date
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- 239000011521 glass Substances 0.000 title claims abstract description 164
- 239000013078 crystal Substances 0.000 claims abstract description 63
- 239000000203 mixture Substances 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 64
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 59
- 239000004973 liquid crystal related substance Substances 0.000 claims description 13
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 9
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 9
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 229910052661 anorthite Inorganic materials 0.000 claims description 5
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 claims description 5
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052863 mullite Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- 229910011255 B2O3 Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 29
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 22
- 239000010408 film Substances 0.000 description 19
- 239000000126 substance Substances 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 230000007423 decrease Effects 0.000 description 13
- 238000000465 moulding Methods 0.000 description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 238000004031 devitrification Methods 0.000 description 11
- 229910052697 platinum Inorganic materials 0.000 description 10
- 239000006060 molten glass Substances 0.000 description 9
- 230000007547 defect Effects 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 238000007500 overflow downdraw method Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 229910021417 amorphous silicon Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000000206 photolithography Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000003280 down draw process Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000006066 glass batch Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000009774 resonance method Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- 206010040925 Skin striae Diseases 0.000 description 1
- 229910006501 ZrSiO Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
- C03C10/0045—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0054—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing PbO, SnO2, B2O3
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/1218—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition or structure of the substrate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/1222—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or crystalline structure of the active layer
- H01L27/1225—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or crystalline structure of the active layer with semiconductor materials not belonging to the group IV of the periodic table, e.g. InGaZnO
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2204/00—Glasses, glazes or enamels with special properties
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133302—Rigid substrates, e.g. inorganic substrates
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
- G02F1/1368—Active matrix addressed cells in which the switching element is a three-electrode device
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
- H10K77/10—Substrates, e.g. flexible substrates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the present invention relates to glass, and more specifically to glass suitable for substrates of organic EL (OLED) displays and liquid crystal displays. Further, the present invention relates to a glass suitable for a substrate of an oxide TFT and a low temperature p-Si.TFT (LTPS) driven display.
- OLED organic EL
- LTPS low temperature p-Si.TFT
- an OLED display or a liquid crystal display driven by LTPS is suitable.
- An OLED display emits light when a current flows through an OLED element constituting a pixel.
- a material having low resistance and high electron mobility is used as the driving TFT element.
- an oxide TFT typified by IGZO (indium, gallium, zinc oxide) has attracted attention.
- An oxide TFT has low resistance and high mobility, and can be formed at a relatively low temperature.
- Conventional p-Si TFTs, especially LTPS form elements on a large-area glass plate due to the instability of an excimer laser used when polycrystallizing an amorphous Si (a-Si) film.
- the TFT characteristics are likely to vary, and screen display unevenness is likely to occur in TV applications.
- an oxide TFT has been attracting attention as an effective TFT forming material because it has excellent uniformity of TFT characteristics when an element is formed on a large-area glass plate, and has already been put into practical use in part.
- the alkali component in the glass is large, alkali ions are diffused into the semiconductor material on which the film is formed during the heat treatment, and the characteristics of the film are deteriorated. Therefore, the content of alkali components (particularly, Li component and Na component) is low or not substantially contained.
- Various chemicals such as acid and alkali are used in the photolithography etching step. Therefore, it has excellent chemical resistance.
- the glass plate is heat-treated at a temperature of several hundred degrees Celsius in steps such as film formation and annealing. When the glass plate is thermally contracted during the heat treatment, pattern deviation or the like is likely to occur. Therefore, heat shrinkage is difficult, especially the strain point is high.
- the coefficient of thermal expansion is close to that of a member (for example, a-Si, p-Si) formed on a glass plate.
- the thermal expansion coefficient is 30 to 40 ⁇ 10 ⁇ 7 / ° C.
- the thermal shock resistance is also improved.
- the Young's modulus (or specific Young's modulus) is high in order to suppress defects caused by the bending of the glass plate.
- the following properties (6) and (7) are required for glass.
- (6) Excellent meltability in order to prevent melting defects such as bubbles, blisters and striae.
- (7) Excellent devitrification resistance to avoid generation of foreign matter in the glass plate.
- the present invention has been made in view of the above circumstances, and its technical problem is to create a glass suitable for LTPS, an OLED display driven by an oxide TFT element, and a liquid crystal display. Specifically, The idea is to create a glass with high devitrification resistance even when the strain point and Young's modulus are high.
- SiO 2 —Al 2 O 3 —B 2 O 3 —RO (RO is one or more of MgO, CaO, SrO, BaO) system. Focusing on glass, it can be found that if the contents of SiO 2 , Al 2 O 3 , B 2 O 3 and RO are optimized, the strain point, Young's modulus, etc. are improved, and SiO 2 -Al is used as the initial phase. When 2 or more kinds of 2 O 3 -RO crystal, SiO 2 crystal, and SiO 2 -Al 2 O 3 crystal are precipitated, the glass is stabilized and the devitrification resistance is remarkably improved. I found out.
- the glass of the present invention contains SiO 2 , Al 2 O 3 , B 2 O 3 and RO as a glass composition, and precipitates in the temperature range from the liquidus temperature (liquidus temperature ⁇ 50 ° C.).
- the liquidus temperature is obtained by passing the standard sieve 30 mesh (500 ⁇ m) and putting the glass powder remaining in 50 mesh (300 ⁇ m) into a platinum boat and holding it in a temperature gradient furnace for 24 hours. The boat is taken out and set to the highest temperature at which devitrification (crystal foreign matter) is observed inside the glass by microscopic observation.
- the “ ⁇ system crystal” refers to a crystal composed of explicit components.
- the SiO 2 —Al 2 O 3 —RO based crystal is preferably a SiO 2 —Al 2 O 3 —CaO based crystal.
- the SiO 2 —Al 2 O 3 —RO based crystal is preferably anorthite
- the SiO 2 based crystal is cristobalite
- the SiO 2 —Al 2 O 3 based crystal is preferably mullite.
- the glass of the present invention preferably has a liquidus temperature lower than 1250 ° C.
- the content of Li 2 O + Na 2 O + K 2 O in the glass composition is less than 0.5 wt%. In this way, it becomes easy to prevent a situation where alkali ions are diffused into the deposited semiconductor material during the heat treatment and the characteristics of the film are deteriorated.
- Li 2 O + Na 2 O + K 2 O refers to the total amount of Li 2 O, Na 2 O and K 2 O.
- the glass of the present invention has a glass composition of mass%, SiO 2 57-70%, Al 2 O 3 16-25%, B 2 O 3 1-8%, MgO 0-5%, CaO 2-13%. , SrO 0-6%, BaO 0-7%, ZnO 0-5%, ZrO 2 0-5%, TiO 2 0-5%, P 2 O 5 0-5%, molar ratio (MgO + CaO + SrO + BaO) / Al 2 O 3 is preferably 0.8 to 1.3, and the molar ratio CaO / Al 2 O 3 is preferably 0.3 to 1.0.
- MgO + CaO + SrO + BaO refers to the total amount of MgO, CaO, SrO and BaO.
- the glass of the present invention as a glass composition, in mass%, SiO 2 58 ⁇ 70% , Al 2 O 3 16 ⁇ 25%, B 2 O 3 2 ⁇ 7%, MgO 0 ⁇ 5%, CaO 3 ⁇ 13% , SrO 0-6%, BaO 0-6%, ZnO 0-5%, ZrO 2 0-5%, TiO 2 0-5%, P 2 O 5 0-5%, SnO 2 0-5%
- the molar ratio (MgO + CaO + SrO + BaO) / Al 2 O 3 is 0.8 to 1.3, the molar ratio CaO / Al 2 O 3 is 0.3 to 1.0, and substantially Li 2 O, Na 2 O. It is preferable not to contain.
- substantially does not contain refers to the case where the content of the explicit component is 0.1% or less (preferably 0.05% or less), for example, “substantially contains Li 2 O”. “No” refers to the case where the content of Li 2 O is 0.1% or less (preferably 0.05% or less).
- the glass of the present invention preferably has a molar ratio CaO / MgO of 2 to 20.
- the glass of the present invention preferably has a strain point of 700 ° C. or higher.
- strain point refers to a value measured based on the method of ASTM C336.
- the glass of the present invention preferably has a Young's modulus of 75 GPa or more. “Young's modulus” refers to a value measured by a dynamic elastic modulus measurement method (resonance method) based on JIS R1602.
- the glass of the present invention preferably has a specific Young's modulus of 30 GPa / (g / cm 3 ) or more.
- specific Young's modulus is a value obtained by dividing Young's modulus by density.
- the glass of the present invention has a flat plate shape and is preferably used for a liquid crystal display.
- the glass of the present invention has a flat plate shape and is preferably used for an OLED display.
- the glass of the present invention has a flat plate shape and is preferably used for an oxide TFT drive display.
- crystals precipitated in the temperature range from the liquidus temperature are SiO 2 —Al 2 O 3 —RO crystal, SiO 2 crystal, SiO 2 —.
- Al 2 O 3 -based crystals it has a property that two or more types of crystals are precipitated, and preferably has a property that three types of crystals are precipitated.
- the glass is stabilized and the liquidus temperature is greatly reduced.
- a glass satisfying the above required characteristics (1) to (7) can be easily obtained if it is a glass in which a plurality of the crystals are precipitated near the liquidus temperature.
- SiO 2 —Al 2 O 3 —RO based crystal SiO 2 —Al 2 O 3 —CaO based crystal is preferable, and anorthite is particularly preferable.
- SiO 2 crystal cristobalite is preferable.
- Mullite is preferred as the SiO 2 —Al 2 O 3 based crystal. If a glass in which a plurality of the crystals are precipitated near the liquidus temperature is obtained, it becomes easier to obtain a glass satisfying the required characteristics (1) to (7), particularly (7).
- the glass of the present invention has a glass composition of mass%, SiO 2 57-70%, Al 2 O 3 16-25%, B 2 O 3 1-8%, MgO 0-5%, CaO 2-13%. , SrO 0-6%, BaO 0-7%, ZnO 0-5%, ZrO 2 0-5%, TiO 2 0-5%, P 2 O 5 0-5%, molar ratio (MgO + CaO + SrO + BaO) / Al 2 O 3 is preferably 0.8 to 1.3, and the molar ratio CaO / Al 2 O 3 is preferably 0.3 to 1.0.
- the reason why the content of each component is regulated as described above will be described below. In addition, in description of each component, the following% display points out the mass% unless there is particular notice.
- the preferred upper limit content of SiO 2 is 70%, 68%, 66% or 65%, especially 64%, and the preferred lower limit content is 57%, 58%, 59% or 60%, especially 61%.
- the most preferable content range is 61 to 64%.
- the content of Al 2 O 3 When the content of Al 2 O 3 is too low, the strain point is lowered, the thermal shrinkage value is increased, the Young's modulus is lowered, and the glass plate is easily bent. On the other hand, if the content of Al 2 O 3 is too high, the BHF (buffered hydrofluoric acid) resistance is lowered, and the glass surface is likely to become cloudy and the crack resistance is liable to be lowered. Furthermore, SiO 2 —Al 2 O 3 -based crystals, particularly mullite, precipitate in the glass, and the liquidus viscosity tends to decrease.
- the preferred upper limit content of Al 2 O 3 is 25%, 23%, 22% or 21%, especially 20%, and the preferred lower limit content is 16%, 17% or 17.5%, In particular, it is 18%. The most preferable content range is 18 to 20%.
- B 2 O 3 is a component that works as a flux and lowers viscosity to improve meltability.
- the content of B 2 O 3 is preferably 1 to 8%, 2 to 8%, 3 to 7.5%, 3 to 7% or 4 to 7%, particularly preferably 5 to 7%.
- the content of B 2 O 3 is too low, it does not sufficiently act as a flux, and the BHF resistance and crack resistance are likely to decrease. In addition, the liquidus temperature is likely to rise.
- the content of B 2 O 3 is too high, the strain point, heat resistance, and acid resistance tend to decrease. In particular, when the content of B 2 O 3 is 7% or more, the tendency becomes remarkable. If the content of B 2 O 3 is too high, it decreases Young's modulus, tends large amount of deflection of the glass plate.
- the mass ratio Al 2 O 3 / B 2 O 3 is preferably 1 to 5, 1.5 to 4.5, or 2 to 4, particularly preferably 2.5 to 3. .5.
- MgO is a component that improves the meltability by lowering the high temperature viscosity without lowering the strain point. MgO has the effect of reducing the density most in RO. However, when it is introduced excessively, SiO 2 -based crystals, particularly cristobalite, are precipitated, and the liquidus viscosity tends to decrease. Further, MgO is a component that easily reacts with BHF or hydrofluoric acid to form a product. This reaction product may adhere to the element on the surface of the glass plate or adhere to the glass plate, causing the element or the glass plate to become cloudy. Therefore, the content of MgO is preferably 0 to 5%, more preferably 0.01 to 4%, still more preferably 0.03 to 3%, and most preferably 0.05 to 2.5%.
- CaO like MgO, is a component that lowers the high temperature viscosity without lowering the strain point and significantly improves the meltability. If the CaO content is too high, SiO 2 -Al 2 O 3 -RO-based crystals, especially anorthite, precipitate, the liquidus viscosity tends to decrease, and the BHF resistance decreases, resulting in a reaction product. There is a possibility that an object sticks to the element on the surface of the glass plate or adheres to the glass plate, causing the element or the glass plate to become cloudy.
- the preferred upper limit content of CaO is 12%, 11% or 10.5%, especially 10%, and the preferred lower limit content is 2%, 3% or 3.5%, especially 4%. is there. The most preferable content range is 4 to 10%.
- the preferable upper limit value of the molar ratio CaO / Al 2 O 3 is 1.0, 0.9, 0.85, 0.8, 0.78 or 0.76, particularly 0.75, and the preferable lower limit value. Is 0.3, 0.4, 0.5, 0.55, 0.58, 0.60, 0.62 or 0.64, in particular 0.65.
- molar ratio CaO / MgO When the molar ratio CaO / MgO is adjusted to a predetermined range, two or more types of crystals are likely to precipitate at a temperature near the liquidus temperature. When the molar ratio CaO / MgO is small, SiO 2 -based crystals are likely to precipitate. On the other hand, when the molar ratio CaO / MgO increases, SiO 2 —Al 2 O 3 —CaO based crystals tend to precipitate.
- a preferable upper limit value of the molar ratio CaO / MgO is 20, 17, 14, 12, 10 or 8, particularly 6, and a preferable lower limit value is 2, 2.5, 2.8, 3.1, 3. 3, 3.5 or 3.8, especially 4.
- SrO is a component that enhances chemical resistance and devitrification resistance. However, if the ratio is excessively increased in the entire RO, the meltability tends to decrease and the density and the thermal expansion coefficient easily increase. . Therefore, the content of SrO is preferably 0 to 6% or 0 to 5%, particularly preferably 0 to 4.5%.
- BaO is a component that enhances chemical resistance and devitrification resistance, but if its content is too high, the density tends to increase. Moreover, BaO has a poor effect of improving the meltability in RO. Glass containing SiO 2 , Al 2 O 3 , B 2 O 3 and RO in the glass composition is generally difficult to melt. Therefore, from the viewpoint of supplying a high-quality glass plate at a low cost and in large quantities, it is necessary to improve the meltability. It is very important to reduce the defect rate due to bubbles, foreign matters and the like. Therefore, the content of BaO is preferably 0 to 7%, 0 to 6% or 0.1 to 5%, particularly preferably 0.5 to 4%.
- MgO, SrO, and BaO have the property of improving crack resistance compared to CaO. Therefore, the content of MgO + SrO + BaO (total amount of MgO, SrO and BaO) is preferably 2% or more or 3% or more, particularly preferably more than 3%. However, if the content of MgO + SrO + BaO is too high, the density and the thermal expansion coefficient tend to increase. Therefore, the content of MgO + SrO + BaO is preferably 9% or less or 8% or less.
- the liquidus temperature is drastically lowered, and it is difficult for crystal foreign matter to be generated in the glass, thereby improving the meltability and formability.
- the content of MgO + CaO + SrO + BaO is preferably less than 15% or less than 14%, particularly preferably less than 13%.
- the preferred upper limit of the molar ratio (MgO + CaO + SrO + BaO) / Al 2 O 3 is 1.3, 1.25, 1.2, 1.15 or 1.10, particularly 1.08, and the preferred lower limit is 0. .8, 0.85, 0.88, 0.91, 0.93, 0.95 or 0.96, especially 0.97.
- the mass ratio CaO / (MgO + SrO + BaO) is preferably 0.7 or more, 0.8 or more or 0.9 or more, particularly preferably 1 or more, and the mass ratio CaO / MgO Is preferably 2 or more, 3 or more, or 4 or more, particularly preferably 5 or more.
- ZnO is a component that improves meltability and BHF resistance. However, if its content is too high, the glass tends to devitrify or the strain point decreases, making it difficult to ensure heat resistance. . Therefore, the content of ZnO is preferably 0 to 5%, particularly preferably 0 to 1%.
- ZrO 2 is a component that enhances chemical durability. However, when the amount of ZrO 2 is increased, devitrification of ZrSiO 4 tends to occur.
- the preferred lower limit of ZrO 2 content is 1%, 0.5%, 0.3% or 0.2%, especially 0.1%, and 0.005% or more is introduced from the viewpoint of chemical durability. It is preferable to do. The most preferable content range is 0.005 to 0.1%.
- ZrO 2 may be introduced from a raw material or may be introduced by elution from a refractory.
- TiO 2 has the effect of lowering the high-temperature viscosity to increase the meltability and the chemical durability, but when the amount introduced is excessive, the ultraviolet transmittance tends to decrease.
- the content of TiO 2 is preferably 3% or less, 1% or less, 0.5% or less, 0.1% or less or 0.05% or less, particularly preferably 0.03% or less. If a very small amount of TiO 2 is introduced (for example, 0.001% or more), an effect of suppressing coloring by ultraviolet rays can be obtained.
- P 2 O 5 is a component that increases the strain point and is effective for precipitating two or more types of crystals by suppressing the precipitation of SiO 2 —Al 2 O 3 —RO-based crystals, particularly anorthite. It is an ingredient. However, when P 2 O 5 is contained in a large amount, the glass is likely to undergo phase separation.
- the content of P 2 O 5 is preferably 0 to 5%, 0 to 3%, 0 to 2% or 0 to 1%, particularly preferably 0 to 0.5%.
- metal powder such as As 2 O 3 , Sb 2 O 3 , SnO 2 , SO 3 , Fe 2 O 3 , CeO 2 , F 2 , Cl 2 , C, Al, Si, or the like can be used. .
- the total content is preferably 3% or less.
- As 2 O 3 and Sb 2 O 3 are environmentally hazardous chemicals, so it is desirable not to use them as much as possible.
- the contents of As 2 O 3 and Sb 2 O 3 are less than 0.3%, less than 0.1%, less than 0.09%, less than 0.05%, less than 0.03%, and less than 0.01%, respectively. Alternatively, it is preferably less than 0.005%, particularly preferably less than 0.003%.
- SnO 2 functions as a fining agent for reducing bubbles in the glass and has an effect of maintaining a relatively high ultraviolet transmittance when coexisting with Fe 2 O 3 or FeO.
- the preferable upper limit content of SnO 2 is 0.5% or 0.4%, particularly 0.3%, and the preferable lower limit content is 0.01% or 0.05%. 1%.
- the content of Fe 2 O 3 or FeO in terms of Fe 2 O 3 is from 0.01 to 0.05%, is introduced to SnO 2 0.01 ⁇ 0.5%, bubble quality and UV transmittance The rate can be increased.
- “Fe 2 O 3 conversion” refers to a value obtained by converting the total Fe amount to the Fe 2 O 3 amount regardless of the valence.
- Iron is a component mixed from the raw material as an impurity, but if the iron content is too high, the ultraviolet transmittance may be lowered. When the ultraviolet transmittance is lowered, there is a possibility that a defect may occur in a photolithography process for manufacturing a TFT or a liquid crystal alignment process using ultraviolet rays. Therefore, the preferable upper limit content of iron is 0.001% in terms of Fe 2 O 3 , and the preferable lower limit content is 0.05% and 0.04% in terms of Fe 2 O 3. Or 0.03%, especially 0.02%. The most preferable content range is 0.001% to 0.02%.
- Cr 2 O 3 is a component mixed from the raw material as an impurity, but if the content of Cr 2 O 3 is too high, light enters from the end face of the glass plate, and the foreign matter inside the glass plate is inspected by scattered light. In such a case, it is difficult to transmit light, and there is a possibility that a defect may occur in the foreign substance inspection. In particular, this problem is likely to occur when the substrate size is 730 mm ⁇ 920 mm or more. Further, the thickness of the glass plate is small (for example 0.5mm or less, 0.4 mm or less, or 0.3mm or less), since the light incident from the glass plate end face is reduced, to restrict the content of Cr 2 O 3 Significance increases.
- the preferable upper limit content of Cr 2 O 3 is 0.001%, 0.0008%, 0.0006% or 0.0005%, particularly 0.0003%, and the preferable lower limit content is 0.00001%. It is.
- the most preferable content range is 0.00001 to 0.0003%.
- Rh 2 O 3 may be mixed from a platinum production container.
- the content of Rh 2 O 3 is preferably 0 to 0.0005%, more preferably 0.00001 to 0.0001%.
- SO 3 is a component mixed from the raw material as an impurity. However, if the content of SO 3 is too high, bubbles called reboil may be generated during melting and molding, which may cause defects in the glass. is there.
- the preferable upper limit content of SO 3 is 0.005%, 0.003% or 0.002%, particularly 0.001%, and the preferable lower limit content is 0.0001%.
- the most preferable content range is 0.0001% to 0.001%.
- Alkaline components particularly Li 2 O and Na 2 O, are preferable to reduce their content to 0.5% in order to degrade the characteristics of various films and semiconductor elements formed on the glass plate. It is desirable not to contain.
- the amount introduced is preferably 5% or less or 3% or less, particularly preferably 1% or less.
- the density is preferably 2.52 g / cm 3 or less, 2.51 g / cm 3 or less, 2.50 g / cm 3 or less or 2.49 g / cm 3 or less, particularly preferably 2.48 / cm 3 or less.
- the density is preferably 2.43 g / cm 3 or more, or 2.44 g / cm 3 or more, particularly preferably 2.45 g / cm 3 or more.
- the thermal expansion coefficient is preferably 30 to 40 ⁇ 10 ⁇ 7 / ° C., 32 to 39 ⁇ 10 ⁇ 7 / ° C., or 33 to 38 ⁇ 10 ⁇ 7 / ° C., particularly preferably 34 to 37. ⁇ 10 -7 / ° C.
- thermal expansion coefficient refers to an average thermal expansion coefficient measured in a temperature range of 30 to 380 ° C., and can be measured, for example, with a dilatometer.
- a large-area glass plate for example, 730 ⁇ 920 mm or more, 1100 ⁇ 1250 mm or more, or 1500 ⁇ 1500 mm or more
- a thin glass plate for example, a plate thickness of 0.1 mm or more. 5 mm or less, 0.4 mm or less, or 0.3 mm or less.
- Specific modulus is preferably 30GPa / g ⁇ cm -3 or more, 30.5GPa / g ⁇ cm -3 or more, or 31GPa / g ⁇ cm -3 or more, and particularly preferably 31.5GPa / g ⁇ cm -3 or more It is. Also, when the glass plate becomes large and thin, warping of the glass plate becomes a problem after a heat treatment process on a surface plate or a film formation process of various metal films, oxide films, semiconductor films, organic films, etc. Become. In order to reduce the warpage of the glass plate, it is effective to increase the Young's modulus of the glass plate.
- the Young's modulus is preferably 75 GPa or more, particularly preferably 76 GPa or more.
- the process temperature of LTPS used in ultra-high-definition mobile displays is about 400-600 ° C.
- the strain point is preferably 680 ° C. or higher or 690 ° C. or higher, particularly preferably 700 ° C. or higher.
- oxide TFTs have been fabricated by a temperature process of 300 to 400 ° C. equivalent to a-Si. However, if annealing is performed at a higher heat treatment temperature than before, more stable device characteristics can be obtained. I understand.
- the heat treatment temperature is about 400 to 600 ° C., and a glass plate with low heat shrinkage is required even in this application.
- the heat shrinkage value is preferably 5 ppm or more, particularly preferably 8 ppm or more.
- the heat shrinkage value can also be reduced by reducing the cooling rate during molding.
- the annealing point of glass be Ta (° C.)
- R (° C./min) be the average cooling rate during molding in the temperature range from a temperature 100 ° C. higher than Ta to a temperature 100 ° C. lower than Ta. upon cooling during molding
- logR ⁇ 0.00018361Ta 2 -0.23414Ta + 75.29 more preferably satisfies the relationship logR ⁇ 0.00011821Ta 2 -0.14847Ta + 47.03
- LogR ⁇ 0.000054326Ta 2 ⁇ 0.064985Ta + 19.56 is more preferably satisfied.
- the heat shrinkage value tends to be excessive.
- molten glass flows down the surface of a wedge-shaped refractory (or a refractory coated with a platinum group metal), joins at the lower end of the wedge, and is formed into a plate shape.
- a ribbon-shaped molten glass is flowed down from a platinum group metal pipe having a slit-shaped opening and cooled to be formed into a plate shape. If the temperature of the molten glass in contact with the forming apparatus is too high, the forming apparatus will be deteriorated, and the productivity of the glass plate will be easily lowered. Therefore, the temperature at a high temperature viscosity of 10 5.0 dPa ⁇ s is preferably 1300 ° C.
- the “temperature at 10 5.0 dPa ⁇ s” can be measured by, for example, a platinum ball pulling method.
- the temperature at a high temperature viscosity of 10 5.0 dPa ⁇ s corresponds to the temperature of the molten glass at the time of molding.
- the temperature at a high temperature viscosity of 10 2.5 dPa ⁇ s is preferably 1650 ° C. or lower, 1640 ° C. or lower, 1630 ° C. or lower, or 1620 ° C.
- the “temperature at 10 2.5 dPa ⁇ s” can be measured by, for example, a platinum ball pulling method.
- the temperature at a high temperature viscosity of 10 2.5 dPa ⁇ s corresponds to the melting temperature, and the lower this temperature, the better the meltability.
- Devitrification resistance is important when molding by the downdraw method or the like.
- the liquidus temperature is preferably less than 1250 ° C., 1230 ° C. or less, 1220 ° C. or less, 1210 ° C. Or 1200 ° C. or less, particularly preferably 1190 ° C. or less.
- the liquidus viscosity is preferably 10 5.0 dPa ⁇ s or more, 10 5.2 dPa ⁇ s or more, 10 5.3 dPa ⁇ s or more, 10 5.4 dPa ⁇ s or more, or 10 5.5 dPa ⁇ s or more, and particularly preferably 10 5.6 dPa ⁇ s or more.
- dPa ⁇ s or more refers to the viscosity of glass at the liquidus temperature, and can be measured by, for example, a platinum ball pulling method.
- a transparent conductive film, an insulating film, a semiconductor film, a metal film, etc. are formed on a glass plate used for a high-definition display. Furthermore, various circuits and patterns are formed by a photolithography etching process. In these film forming process and photolithography etching process, the glass plate is subjected to various chemical treatments. For example, in a TFT type active matrix liquid crystal display, an insulating film or a transparent conductive film is formed on a glass plate, and a large number of amorphous silicon or polycrystalline silicon TFTs (thin film transistors) are formed on the glass plate by a photolithography etching process.
- the glass of the present invention is preferably formed by an overflow down draw method.
- the overflow down draw method is a method in which molten glass is overflowed from both sides of a wedge-shaped refractory, and the overflowed molten glass is merged at the lower end of the wedge shape, and is stretched downward to form a glass plate.
- the surface to be the surface of the glass plate is not in contact with the refractory, and is formed in a free surface state. For this reason, it is possible to produce an unpolished glass plate with good surface quality at low cost, and it is easy to increase the area and thickness.
- the material of the refractory used in the overflow downdraw method is not particularly limited as long as it can realize desired dimensions and surface accuracy.
- the method of applying a force when performing downward stretch molding is not particularly limited.
- a method may be adopted in which a heat-resistant roll having a sufficiently large width is rotated and stretched in contact with the glass, or a plurality of pairs of heat-resistant rolls are contacted only near the end face of the glass. It is also possible to adopt a method of stretching by stretching.
- a glass plate can be formed by, for example, a downdraw method (slot down method, redraw method, etc.), a float method, or the like.
- the thickness is not particularly limited, but is preferably 0.5 mm or less, 0.4 mm or less, or 0.35 mm or less, particularly preferably 0.3 mm or less.
- the smaller the plate thickness the easier it is to reduce the weight of the device.
- the smaller the plate thickness the easier the glass plate bends.
- board thickness can be adjusted with the flow rate at the time of glass manufacture, a board drawing speed, etc.
- the strain point can be increased by lowering the ⁇ -OH value.
- the ⁇ -OH value is preferably 0.5 / mm or less, 0.45 / mm or less or 0.4 / mm or less, particularly preferably 0.35 / mm or less. If the ⁇ -OH value is too large, the strain point tends to decrease. If the ⁇ -OH value is too small, the meltability tends to be lowered. Therefore, the ⁇ -OH value is preferably 0.01 / mm or more, particularly preferably 0.05 / mm or more.
- the following methods may be mentioned.
- a component (Cl, SO 3 or the like) that lowers the ⁇ -OH value is added to the glass.
- (4) N 2 bubbling is performed in molten glass.
- Adopt a small melting furnace. Increase the flow rate of the molten glass. (7) An electric melting method is adopted.
- ⁇ -OH value refers to a value obtained by measuring the transmittance of glass using FT-IR and using the following equation.
- ⁇ -OH value (1 / X) log (T 1 / T 2 )
- X Glass wall thickness (mm)
- T 1 Transmittance (%) at a reference wavelength of 3846 cm ⁇ 1
- T 2 Minimum transmittance (%) in the vicinity of a hydroxyl group absorption wavelength of 3600 cm ⁇ 1
- the glass of the present invention is preferably used for an OLED display substrate. OLEDs are generally being marketed, but cost reduction by mass production is strongly desired. Since the glass of the present invention is excellent in productivity and can be easily increased in area and thickness, such a requirement can be satisfied accurately.
- Tables 1 to 3 show examples of the present invention (sample Nos. 1 to 30).
- Each sample was produced as follows. First, a glass batch in which glass raw materials were prepared so as to have the glass composition in the table was placed in a platinum crucible and melted at 1600 ° C. for 24 hours. In melting the glass batch, the mixture was stirred and homogenized using a platinum stirrer. Next, the molten glass was poured out on a carbon plate and formed into a plate shape.
- the density is a value measured by the well-known Archimedes method.
- the thermal expansion coefficient is an average thermal expansion coefficient measured with a dilatometer in a temperature range of 30 to 380 ° C.
- the Young's modulus refers to a value measured by a dynamic elastic modulus measurement method (resonance method) based on JIS R1602, and the specific Young's modulus is a value obtained by dividing Young's modulus by density.
- strain point and softening point are values measured by the fiber elongation method based on the method of ASTM C336.
- the temperature at a high temperature viscosity of 10 2.5 dPa ⁇ s and 10 5.0 dPa ⁇ s is a value measured by a platinum ball pulling method.
- each sample was pulverized, passed through a standard sieve 30 mesh (500 ⁇ m), and the glass powder remaining on 50 mesh (300 ⁇ m) was placed in a platinum boat and held in a temperature gradient furnace for 24 hours.
- the highest temperature at which devitrification (crystal foreign matter) was observed inside the glass by microscopic observation was taken as the liquidus temperature.
- crystals precipitated in the temperature range from the liquidus temperature were evaluated as the initial phase.
- “Ano” indicates an anosite
- “Cri” indicates cristobalite
- “Mul” indicates mullite.
- the viscosity of the glass at the liquidus temperature was measured by the platinum ball pulling method, and this was defined as the liquidus viscosity.
- the surface of the obtained sample is observed to be chemically resistant. Evaluated. Specifically, after chemical treatment, the glass surface is strongly clouded or cracked, “X”, those with weak cloudiness and roughness are “ ⁇ ”, and those with no change are “O”. It was. As conditions for chemical treatment, acid resistance was evaluated by treatment at 80 ° C. for 3 hours using 10% by mass hydrochloric acid, and BHF resistance was evaluated by treatment at 20 ° C. for 30 minutes using a well-known 130 BHF solution. .
- Sample No. Nos. 1 to 30 have a density of 2.45 to 2.48 g / cm 3 , which can reduce the weight of the glass plate. Further, the thermal expansion coefficient is 33 to 37 ⁇ 10 ⁇ 7 / ° C. and the strain point is 702 ° C. or higher, so that the heat shrinkage value can be reduced. In addition, the Young's modulus is 75 GPa or more and the specific Young's modulus is 30.3 GPa / (g / cm 3 ) or more, so that bending and deformation hardly occur. The temperature at a high temperature viscosity of 10 2.5 dPa ⁇ s is 1678 ° C.
- the temperature at a high temperature viscosity of 10 5.0 dPa ⁇ s is 1250 ° C. or lower
- the liquidus temperature is 1230 ° C. or lower
- the liquidus viscosity is 10 4.8 dPa ⁇ s. Since it is more than s, it has excellent meltability and moldability, and is suitable for mass production. Furthermore, chemical resistance is also excellent.
- the glass of the present invention can remarkably improve devitrification resistance even when the strain point and Young's modulus are high. Therefore, the glass of the present invention is suitable for a substrate of a display such as an OLED display or a liquid crystal display, and is suitable for a substrate of a display driven by LTPS or an oxide TFT.
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Abstract
Description
(2)フォトリソグラフィーエッチング工程では、種々の酸、アルカリ等の薬液が使用される。よって、耐薬品性に優れていること。
(3)成膜、アニール等の工程で、ガラス板は数百℃の温度に熱処理される。熱処理の際に、ガラス板が熱収縮すると、パターンズレ等が発生し易くなる。よって、熱収縮し難いこと、特に歪点が高いこと。
(4)熱膨張係数が、ガラス板上に成膜される部材(例えば、a-Si、p-Si)に近いこと。例えば、熱膨張係数が30~40×10-7/℃であること。なお、熱膨張係数が40×10-7/℃以下であると、耐熱衝撃性も向上する。
(5)ガラス板の撓みに起因する不具合を抑制するために、ヤング率(又は比ヤング率)が高いこと。 (1) When the alkali component in the glass is large, alkali ions are diffused into the semiconductor material on which the film is formed during the heat treatment, and the characteristics of the film are deteriorated. Therefore, the content of alkali components (particularly, Li component and Na component) is low or not substantially contained.
(2) Various chemicals such as acid and alkali are used in the photolithography etching step. Therefore, it has excellent chemical resistance.
(3) The glass plate is heat-treated at a temperature of several hundred degrees Celsius in steps such as film formation and annealing. When the glass plate is thermally contracted during the heat treatment, pattern deviation or the like is likely to occur. Therefore, heat shrinkage is difficult, especially the strain point is high.
(4) The coefficient of thermal expansion is close to that of a member (for example, a-Si, p-Si) formed on a glass plate. For example, the thermal expansion coefficient is 30 to 40 × 10 −7 / ° C. When the thermal expansion coefficient is 40 × 10 −7 / ° C. or less, the thermal shock resistance is also improved.
(5) The Young's modulus (or specific Young's modulus) is high in order to suppress defects caused by the bending of the glass plate.
(6)泡、ブツ、脈理等の溶融欠陥を防止するために、溶融性に優れていること。
(7)ガラス板中の異物発生を避けるために、耐失透性に優れていること。 Furthermore, from the viewpoint of producing a glass plate, the following properties (6) and (7) are required for glass.
(6) Excellent meltability in order to prevent melting defects such as bubbles, blisters and striae.
(7) Excellent devitrification resistance to avoid generation of foreign matter in the glass plate.
β-OH値 = (1/X)log(T1/T2)
X:ガラス肉厚(mm)
T1:参照波長3846cm-1における透過率(%)
T2:水酸基吸収波長3600cm-1付近における最小透過率(%) Here, “β-OH value” refers to a value obtained by measuring the transmittance of glass using FT-IR and using the following equation.
β-OH value = (1 / X) log (T 1 / T 2 )
X: Glass wall thickness (mm)
T 1 : Transmittance (%) at a reference wavelength of 3846 cm −1
T 2 : Minimum transmittance (%) in the vicinity of a hydroxyl group absorption wavelength of 3600 cm −1
Claims (14)
- ガラス組成として、SiO2、Al2O3、B2O3及びRO(ROは、MgO、CaO、SrO、BaOの内、1種類又は2種類以上)を含み、且つ液相線温度から(液相線温度-50℃)の温度範囲において、析出する結晶が、SiO2-Al2O3-RO系結晶、SiO2系結晶、SiO2-Al2O3系結晶の内、2種類以上であることを特徴とするガラス。 As glass composition, it contains SiO 2 , Al 2 O 3 , B 2 O 3 and RO (RO is one or more of MgO, CaO, SrO and BaO), and from the liquidus temperature (liquid In the temperature range of the phase line temperature (-50 ° C.), two or more kinds of crystals are precipitated out of SiO 2 —Al 2 O 3 —RO crystal, SiO 2 crystal, and SiO 2 —Al 2 O 3 crystal. Glass characterized by being.
- SiO2-Al2O3-RO系結晶が、SiO2-Al2O3-CaO系結晶であることを特徴とする請求項1に記載のガラス。 2. The glass according to claim 1, wherein the SiO 2 —Al 2 O 3 —RO based crystal is a SiO 2 —Al 2 O 3 —CaO based crystal.
- SiO2-Al2O3-RO系結晶がアノーサイト、SiO2系結晶がクリストバライト、SiO2-Al2O3系結晶がムライトであることを特徴とする請求項1に記載のガラス。 2. The glass according to claim 1, wherein the SiO 2 —Al 2 O 3 —RO based crystal is anorthite, the SiO 2 based crystal is cristobalite, and the SiO 2 —Al 2 O 3 based crystal is mullite.
- 液相線温度が1250℃より低いことを特徴とする請求項1~3の何れか1項に記載のガラス。 The glass according to any one of claims 1 to 3, wherein the liquidus temperature is lower than 1250 ° C.
- ガラス組成中のLi2O+Na2O+K2Oの含有量が0.5質量%以下であることを特徴とする請求項1~4の何れか1項に記載のガラス。 5. The glass according to claim 1, wherein the content of Li 2 O + Na 2 O + K 2 O in the glass composition is 0.5% by mass or less.
- ガラス組成として、質量%で、SiO2 57~70%、Al2O3 16~25%、B2O3 1~8%、MgO 0~5%、CaO 2~13%、SrO 0~6%、BaO 0~7%、ZnO 0~5%、ZrO2 0~5%、TiO2 0~5%、P2O5 0~5%を含有し、モル比(MgO+CaO+SrO+BaO)/Al2O3が0.8~1.3、モル比CaO/Al2O3が0.3~1.0であることを特徴とする請求項1~5の何れか1項に記載のガラス。 As glass composition, SiO 2 57-70%, Al 2 O 3 16-25%, B 2 O 3 1-8%, MgO 0-5%, CaO 2-13%, SrO 0-6% by mass%. , BaO 0 to 7%, ZnO 0 to 5%, ZrO 2 0 to 5%, TiO 2 0 to 5%, P 2 O 5 0 to 5%, and the molar ratio (MgO + CaO + SrO + BaO) / Al 2 O 3 is The glass according to any one of claims 1 to 5, wherein 0.8 to 1.3 and a molar ratio CaO / Al 2 O 3 is 0.3 to 1.0.
- ガラス組成として、質量%で、SiO2 58~70%、Al2O3 16~25%、B2O3 2~7%、MgO 0~5%、CaO 3~13%、SrO 0~6%、BaO 0~6%、ZnO 0~5%、ZrO2 0~5%、TiO2 0~5%、P2O5 0~5%、SnO2 0~5%を含有し、モル比(MgO+CaO+SrO+BaO)/Al2O3が0.8~1.3、モル比CaO/Al2O3が0.3~1.0であり、実質的にLi2O、Na2Oを含有しないことを特徴とする請求項1~6の何れか1項に記載のガラス。 As a glass composition, SiO 2 58 to 70%, Al 2 O 3 16 to 25%, B 2 O 3 2 to 7%, MgO 0 to 5%, CaO 3 to 13%, SrO 0 to 6% by mass%. , BaO 0-6%, ZnO 0-5%, ZrO 2 0-5%, TiO 2 0-5%, P 2 O 5 0-5%, SnO 2 0-5%, molar ratio (MgO + CaO + SrO + BaO ) / Al 2 O 3 is 0.8 to 1.3, molar ratio CaO / Al 2 O 3 is 0.3 to 1.0, and is substantially free of Li 2 O and Na 2 O. The glass according to any one of claims 1 to 6.
- モル比CaO/MgOが2~20であることを特徴とする請求項1~7の何れか1項に記載のガラス。 The glass according to any one of claims 1 to 7, wherein the molar ratio CaO / MgO is 2 to 20.
- 歪点が700℃以上であることを特徴とする請求項1~8の何れか1項に記載のガラス。 The glass according to any one of claims 1 to 8, which has a strain point of 700 ° C or higher.
- ヤング率が75GPa以上であることを特徴とする請求項1~9の何れか1項に記載のガラス。 The glass according to any one of claims 1 to 9, wherein Young's modulus is 75 GPa or more.
- 比ヤング率が30GPa/(g/cm3)以上であることを特徴とする請求項1~10の何れか1項に記載のガラス。 The glass according to any one of claims 1 to 10, wherein the specific Young's modulus is 30 GPa / (g / cm 3 ) or more.
- 平板形状であり、液晶ディスプレイに用いることを特徴とする請求項1~11の何れか1項に記載のガラス。 The glass according to any one of claims 1 to 11, which has a flat plate shape and is used for a liquid crystal display.
- 平板形状であり、OLEDディスプレイに用いることを特徴とする請求項1~11の何れか1項に記載のガラス。 The glass according to any one of claims 1 to 11, which has a flat plate shape and is used for an OLED display.
- 平板形状であり、酸化物TFT駆動のディスプレイに用いることを特徴とする請求項1~13の何れか1項に記載のガラス。 The glass according to any one of claims 1 to 13, which has a flat plate shape and is used for an oxide TFT drive display.
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